C(sp3)–H Bond Activation Induced by Monohydroborane Coordination at an Iridium(III)–Phosphoramidate Complex. Issue 20 (13th February 2017)

• Record Type: Journal Article
• Authors: Drover, Marcus W.; Christopherson, Cheyenne J.; Schafer, Laurel L.; Love, Jennifer A.
• Is Part Of: European journal of inorganic chemistry. Issue 20(2017)
• Page Start: 2639
• Page End: 2642
• Publication Date: 2017-02-13
• Subjects: C–H activation -- Cyclometalation -- Iridium -- Boranes -- Diastereoselectivity; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201601518
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The reaction of Cp*Ir III phosphoramidate (Cp* = pentamethylcyclopentadienyl) complexes with a monohydroborane (HBR2 ; R = cyclohexyl or mesityl) generates cyclometalated Cp*Ir III complexes following two sequential intramolecular B–H and C(sp 3 )–H bond‐activation events. Preliminary mechanistic inquiry suggests that boron stabilization provided by the hemilabile phosphoramidate ligand provides a δ ‐B–H··· [Ir] coordinated intermediate, which succumbs to borane‐induced C(sp 3 )–H bond activation. Abstract : Two is better than one to generate cyclometalated Cp*Ir III phosphoramidate complexes by sequential intramolecular B–H and C(sp 3 )–H bond‐activation events. Such complexes represent a first step in an overall Ir‐catalyzed process for organophosphate functionalization. Cp* = pentamethylcyclopentadienyl; Mes = mesityl.